Nitrated products and process of making same.



EDWARD ARTHUR BARNES; or GIANT, CALIFORNIA,

NITRATED PRODUCT AND PROCESS OF MAKING SAME. I

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No Drawing.

To all'wkom it may concern:

Be it known that I, EDWARD A. BAnNEs,a subject of the King of England,residing at Giant, in the county of Contra Costa and State ofCalifornia, have invented new and useful Improvements in NitratedProducts and Processes of Making Same, of which the,

following is a specification.

My invention relates to the separation and isolation of variousconstituents found in natural petroleum oils; and its object is toobtain the aromatic (benzenoid) hydrocarbons in a directly usable formas mononitro-derivatives which, by further treatment, may be obtained ina form fit for commercial use.

The natural petroleum oils, from whatever field they are derived, areknown-to contain a considerable percentage of aromatic, and otherunsaturated cyclic, hydrocarbons, and these compounds greatly desludge.

In my inventionI obtain the above aromatic hydrocarbons in a directlyusable form as mono-nitro-derivatives, which can be fractionallydistilled so as to separate the various mono -nitro-derivatives, whichare thus obtained in a form fit for commercial use in the manufacture ofanilin dyesand explosives.

As a rule the crude oils or distillates which are to be treated containa preponderance of saturated hydrocarbons and a smaller amount ofbenzenoid hydrocarbons. When dealing with crude oils, a preliminarydistillation is necessary to free them from excessive impurities, butthe resulting distillates merely require agitating with cold sulfuricacid to remove the unsaturated hydrocarbons. The percentage of sulfuricSpecification 5r Letters Patent.

" Application filed October 11, 1915. Serial Nd. 55.329.

discoloration is produced and shrinkage of the bulk of the distillateceases.

This cleaned distillate is then nit-rated with a mixture of nitric acidand sulfuric acid at as low a temperature as possible,

when the whole of the aromatic hydrocarbons is obtained asmono-nitro-derivatives.

,I take a mixture of '625 gramsof nitric acid 70% and 325 grams ofsulfuric acid 96%, and run this in a fine stream into about fivethousand grams of cleaned distillate contained in a vessel provided witha stirring device and cooling coils. The temperature is kept as low aspossible and agitation continued for four hours after the acid is in,when the contents are allowedto separate. Three layers are formed, thetop one consisting of cleaned parafiin distillate, the second about thebulk of the first consisting of nitro-aromatic hydrocarbons, and thethird of waste acidsw -These latter should not "contain more than 13% ofunused nitric acid, and excess will show that too great a proportion ofmixed acid was used and work is regulated on this basis. Considerablevariation may be allowed in proportion and strength of mixed acid, butthe one given is found sufiiciently strong to serve its purposeeconomically.

These nitrated compounds separate cleanly forming an intermediate layerbetween the acid and the distillate, which latter is obtained in a muchpurer state than that ohtained by oleum treatment. The mixture ofnitro-aromatic hydrocarbons which represents 10% to 15% of the'originalamount of distillate, dependent on the oil field from which it wasderived, can be fractionally separated in any suitable apparatus, andthese fractions severally reduced to their corresponding'amidoderivatives and used as such in the. manufacture of anilin dyes.

Further, I find that the. complex mixture of mono-nitro-derivativesobtained in this treatment of crude oils and distillates has theproperty of dissolving in nitroglycerin and considerably reducing itsfreezing point, and that this property is also possessed by the mixtureof di-nitro-derivatives obtained by re-nitrating the mixture ofmono-nitroderivatives with stronger acids at a higher temperature, andagain possessed by the mixture of tri-nitro-derivatives obtained byre-nitrating the mixture of di-nitro-deriva- Patented, Jul 23, 1918;

tives with still stronger acids at still higher which range from liquidsto solids are extremely suitable for employment in the manufacture oflow freezing explosives.

The'inixed' acid I employ for renitrating the mixtureofmono-nitro-derivatives has 'a composition of 36% of HNO 62% of H 30and 2% of H and the temperatu're of reaction is maintained at 7centrigrade.

The mixed acid I employ for renitrating the mixture of di-nitroderivatives is the.

strongest attainable, made by mixing" 93% of HNQ; with oleum containingor more et S0 and the temperatureof the reaction is maintained between100 and 125 centigrade. Variations in all these mixtures is allowablebut are not economical.

Having thus described my invention, what I claim and desire to'secure byLetters Patent is-.

'1. -The process which comprises gradually rated hydrocarbons and asmaller amount of locnzcnoid hydrocarbons by treating the oil at a'lowtemperature with suitable proportions ofaniixturc of nitric and sulfuricacids, and separating the mixture of nitroderlvatlves from the remalnlngOll.

bons, nitro benzenoid 3. The process of treating a partly purifiedpetroleum' distillate containing saturated hydrocarbons and a smalleramount of benzenoid hydrocarbons and obtainable by distillin gcrudepetroleum to separate as a residue certain impurities, agitatin thedistillate with a small proportion o sulfuric acid, allowing the mixtureto settle and removing the waste-acid with impurities of the distillatecontained thereimwhich comprises gradually -adding a mixture of nitricand sulfuric acidscontaining a small proportion of water to thepurified, distillate while stirring and cooling the same, allowingthemixture to settle 111130 distinct strata comprising respectivelylparaffin hydrocariydrocarbons and Waste acids, and separating saidnitro-benzenoid hydrocarbons. v

4. The process which comprises treating at a low temperature petroleuoils containing saturated hydrocarbons and a smaller amount of benzenoidhydrocarbons With a mild nitrating agent comprising nitric acid,

sulfuric acid and water to convert benzenoid hydrocarbons in the oilmainly into their mono-nitro-derivatives, separating thenitroderivatives and treating them with a stronger nitrating agent at ahigher temperature to produce polynitro derivatives of said benzenoidhydrocarbons.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

' EDWARD ARTHUR BARNES,

W itnesses GEo. H. STRONG, JOHN H. HERRI G.

copics f this patent may be obtained for five cents each, by addressingthe "Commissioner of Patents,

" Washington, D. 0."

